JPH02180903A - Crosslinked chitosan - Google Patents
Crosslinked chitosanInfo
- Publication number
- JPH02180903A JPH02180903A JP63335055A JP33505588A JPH02180903A JP H02180903 A JPH02180903 A JP H02180903A JP 63335055 A JP63335055 A JP 63335055A JP 33505588 A JP33505588 A JP 33505588A JP H02180903 A JPH02180903 A JP H02180903A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- formula
- chitosan
- partially substituted
- formulas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 5
- -1 ester compound Chemical class 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 6
- 229920002101 Chitin Polymers 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 230000006196 deacetylation Effects 0.000 abstract description 2
- 238000003381 deacetylation reaction Methods 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960002442 glucosamine Drugs 0.000 description 2
- MSWZFWKMSRAUBD-IVMDWMLBSA-N glucosamine group Chemical group OC1[C@H](N)[C@@H](O)[C@H](O)[C@H](O1)CO MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- ZHQLTKAVLJKSKR-UHFFFAOYSA-N homophthalic acid Chemical compound OC(=O)CC1=CC=CC=C1C(O)=O ZHQLTKAVLJKSKR-UHFFFAOYSA-N 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OYUWHGGWLCJJNP-UHFFFAOYSA-N 1,2-Dihydrophthalic acid Chemical compound OC(=O)C1C=CC=CC1C(O)=O OYUWHGGWLCJJNP-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GDYYIJNDPMFMTB-UHFFFAOYSA-N 2-[3-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC(CC(O)=O)=C1 GDYYIJNDPMFMTB-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- QJGNSTCICFBACB-UHFFFAOYSA-N 2-octylpropanedioic acid Chemical compound CCCCCCCCC(C(O)=O)C(O)=O QJGNSTCICFBACB-UHFFFAOYSA-N 0.000 description 1
- OXTNCQMOKLOUAM-UHFFFAOYSA-N 3-Oxoglutaric acid Chemical compound OC(=O)CC(=O)CC(O)=O OXTNCQMOKLOUAM-UHFFFAOYSA-N 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、キトサンとＮ−ヒドロキシイミドエステル化
合物とを反応させて得られる架橋キトサンに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to crosslinked chitosan obtained by reacting chitosan and an N-hydroxyimide ester compound.
［従来の技術］
キトサンはキチン（多くはかに等甲殻類の殻から採取さ
れている）を脱アセチル化して得られる多糖類の一種で
分子内に多くのアミノ基を持っている。[Prior Art] Chitosan is a type of polysaccharide obtained by deacetylating chitin (mostly collected from the shells of crustaceans such as crabs) and has many amino groups in its molecule.
キトサンの性質としては、希酸の水溶液に溶解すること
、生態適合性や生分解性に優れていること、保水性であ
ること、低カロリーであることなどが知られている。こ
れらの性質を利用して廃水処理におけるカチオン系凝集
剤やろ過動剤としてすでに実用化されており、さらに人
口皮膚などの医薬関連分野のほか、化粧品９食品などの
分野にも幅広く検討が行われている。Chitosan is known to have properties such as being soluble in dilute acid aqueous solutions, having excellent ecological compatibility and biodegradability, being water retentive, and being low in calories. Utilizing these properties, it has already been put into practical use as a cationic flocculant and filtration agent in wastewater treatment, and is also being widely studied in fields such as pharmaceuticals such as artificial skin, as well as cosmetics and foods. ing.
［発明が解決しようとする課題］
しかしながら、キトサンは希酸以外には溶解しないこと
、物理的性質としては剛直で柔軟性に欠けるなどのため
に、十分には有効利用されているとはいえないのが現状
である。[Problems to be solved by the invention] However, chitosan cannot be said to be fully utilized effectively because it does not dissolve in anything other than dilute acids, and its physical properties are rigid and lack flexibility. is the current situation.
本発明の目的は、前記のキトサンの利点をいかしながら
、柔軟性、熱や薬品などに対する安定性を持たせ、より
広範囲に利用できる物質を提供することである。The purpose of the present invention is to provide a material that can be used in a wider range of applications by making use of the advantages of chitosan described above while imparting flexibility and stability against heat and chemicals.
［課題を解決するための手段］
本発明は、キトサンと一般式［Ｉ］で表されるＮ−ヒド
ロキシイミドエステル化合物とを反応させて得られる架
橋キトサンである。[Means for Solving the Problems] The present invention is a crosslinked chitosan obtained by reacting chitosan with an N-hydroxyimide ester compound represented by the general formula [I].
Ａはオキシエチレン基、オキシプロピレン基およびオキ
シブチレン基から選ばれる、１種または２種以上の混合
語基、
Ｙは二塩基酸残基、
Ｚは
およびその部分置換体、
およびその部分置換体。A is one or more mixed groups selected from oxyethylene group, oxypropylene group and oxybutylene group, Y is a dibasic acid residue, Z is and a partially substituted product thereof, and a partially substituted product thereof.
す （ただし式中。vinegar (However, during the ceremony.
Ｘは炭素数が２〜６で、２〜６個の水酸基を持つ化合物
の残基、
およびその部分置換体、
（４）式 ［■コ ゝ”ＣＩ（
とＨ
／
およびその部分置換体、
（５） 式 ［■コ
＼
Ｈ２
／ＣＩ−（・
およびその部分置換体、
（６）式［Ｘ１ｆｌ ］
＼
ｌ１２
電
ＣＩ−Ｉ ２
【
／ＣＩ（・
およびその部分置換体から選ばれる基、１１１は１〜５
００、
ｆｌは２〜６
を示す。）
本発明で使用されるキトサンはキチンの脱アセチル化体
で、グルコサミンがβ−１，４型に結合した多糖類（１
，４）−２−アミノ−２デオキシ−β−Ｄ−グルコサミ
ンである。X is a residue of a compound having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups, and a partially substituted product thereof, (4) Formula [■Coゝ”CI( and H / and a partially substituted product thereof, 5) Formula [■ko\H2 /CI-(・ and its partially substituted product, (6) Formula [X1fl] \ l12 Electron CI-I 2 [ /CI(・ and its partially substituted product, 111 is a group selected from 1-5
00, fl indicates 2-6. ) The chitosan used in the present invention is a deacetylated form of chitin, which is a polysaccharide in which glucosamine is bonded to β-1,4 type (1
, 4)-2-amino-2deoxy-β-D-glucosamine.
キチンはＮ−アセチル化り−グルコサミンがβ−１，４
で結合したもので、一般式［ＬＸ］で表される。Chitin is N-acetylated and glucosamine is β-1,4
It is expressed by the general formula [LX].
およびその部分置換体、ならびに
（７） 式 〔■コ
＼
ＣＩ−（
Ｈ
【
７ぶＩＩ・
（式中、ｐ は１０〜５００である。）キトサンとして
は、キチンの脱アセチル化度が４０〜１００％、好まし
くは７０〜１００％のものが使用できる。例えば、キト
サンＰＳＨ［焼津水産（株）商品名、脱アセチル化度８
５％以上コなどがある。and partially substituted products thereof, and (7) formula [■ko\CI-(H[7buII- (in the formula, p is 10 to 500). 100%, preferably 70 to 100% chitosan PSH [trade name of Yaizu Suisan Co., Ltd., deacetylation degree 8] can be used.
5% or more.
本発明で使用するＮ−ヒドロキシイミドエステル化合物
は架橋剤として用いられるもので、」二記の一般式［Ｉ
］でしめされる化合物（以下、架橋剤 と記す。）であ
る。The N-hydroxyimide ester compound used in the present invention is used as a crosslinking agent, and is represented by the general formula [I
] (hereinafter referred to as a crosslinking agent).
一般式［Ｉ］において、Ｘは炭素数が２〜６で、２〜６
個の水酸基を持つ化合物、例えばエチレングリコール、
プロピレングリコール、グリセリン、ジグリセリン、ト
リメチロールエタン、トリメチロールプロパン、ペンタ
エリトリトール、エリトリトール、ソルビ１−−ル、マ
ンニトール、グルコース、マンノース、キシロース、ソ
ルビタンなどから生ずるアルコール残基であり、ｎはこ
れらのアルコールの水酸基に対応して、２〜６の値を示
す。In general formula [I], X has 2 to 6 carbon atoms, and 2 to 6
Compounds with hydroxyl groups, such as ethylene glycol,
An alcohol residue derived from propylene glycol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, erythritol, sorbitol, mannitol, glucose, mannose, xylose, sorbitan, etc., and n is one of these alcohols. It shows a value of 2 to 6 corresponding to the hydroxyl group.
Ａはオキシエチレン基、オキシプロピレン基、オキシブ
チレン拮からえらばれる１種または２種以上の混合基で
、２種以上のときはブロック状に付加していてもランダ
ム状に付加していてもよく、Ｉｎはその平均付加モル数
を示す。A is one type or a mixture of two or more groups selected from oxyethylene group, oxypropylene group, and oxybutylene group, and when two or more types are used, it may be added in a block form or randomly. , In indicates the average number of moles added.
Ｙは二塩基酸、例えば、シュウ酸、マロン酸。Y is a dibasic acid, such as oxalic acid, malonic acid.
コハク酸、グルタル酸、アジピン酸、ピメリン酸、コル
ク酸、アゼライン酸、セバシン酸、ノナンジカルボン酸
、デカンジカルボン酸、ウンデカンジカルボン酸、イソ
コハク酸、メチルコハク酸、エチルマロン酸、ジメチル
マロン酸、リンゴ酸、タルトロン酸、マレイン酸、フマ
ール酸、オキサル酢酸、酒石酸、メソシュウ酸、アセト
ンジカルボン酸、シトラコン酸、メサコン酸、イタコン
酸、フタル酸、イソフタル酸、テレフタル酸、ホモフタ
ル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、
ジヒドロフタル酸、０−フェニレン酢酸、ｍ−フェニレ
ンニ酢酸５ｐ−フェニレンニ酢酸、０−フェニレン酢酸
−β−プロピオン酸、ナフタレン−２，３−ジカルボン
酸、ナフタレン−１，２−ジカルボン酸、ナフタレン−
１，８−ジカルボン酸、ジフェン酸、アスパラギン酸、
グルタミン酸、α−ケトグルタル酸、α−オキシグルタ
ル酸、などの二塩基酸の残基を示す。Succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, isosuccinic acid, methylsuccinic acid, ethylmalonic acid, dimethylmalonic acid, malic acid, Tartronic acid, maleic acid, fumaric acid, oxalacetic acid, tartaric acid, mesooxalic acid, acetone dicarboxylic acid, citraconic acid, mesaconic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid ,
Dihydrophthalic acid, 0-phenyleneacetic acid, m-phenylenediacetic acid, 5p-phenylenediacetic acid, 0-phenyleneacetic acid-β-propionic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-
1,8-dicarboxylic acid, diphenic acid, aspartic acid,
Indicates a residue of a dibasic acid such as glutamic acid, α-ketoglutaric acid, α-oxyglutaric acid, etc.
Ｚは前記式［Ｉ］］〜［■］の構造の外、その部分置換
体として、例えば 式［Ｉ］１の場合、式［■］の場合
。In addition to the structures of formulas [I] to [■], Z is a partially substituted product thereof, such as in the case of formula [I]1 and in the case of formula [■].
式［Ｖ］の場合、 式［ＶＩ］の場合、 などの構造を含むものである。In the case of formula [V], In the case of formula [VI], It includes structures such as.
以上の各構造から成る一般式［Ｉ］の架橋剤は、キトサ
ンのアミノ基、と特異的に反応する際、Ｎ−ヒドロキシ
イミドを遊離するとともにキトサンのアミノ基と反応し
て付加生成物を作るので、下記例に示すようにキ１−サ
ンのアミノ基に対して架橋剤として働き、常温、水溶液
中で架橋反応を行い。When the crosslinking agent of general formula [I] having each of the above structures reacts specifically with the amino group of chitosan, it liberates N-hydroxyimide and reacts with the amino group of chitosan to form an addition product. Therefore, as shown in the example below, it acts as a crosslinking agent for the amino group of x1-san and performs a crosslinking reaction in an aqueous solution at room temperature.
キトサンを高分子化してゲルを形成する。Polymerize chitosan to form a gel.
上記の反応において、Ｘがエチレングリコール、プロピ
レングリコールなどのジオールから生じるアルコール残
基の場合、ｎは２であって、架橋剤は２官能と成り、比
較的柔らかいゲルを形成する。In the above reaction, when X is an alcohol residue generated from a diol such as ethylene glycol or propylene glycol, n is 2, the crosslinking agent becomes difunctional, and a relatively soft gel is formed.
またＸがペンタエリトリトールまたはソルビトールなど
のポリオールから生ずるアルコール残基の場合には、ｎ
は４または６であって架橋剤は多官能と成り、これらに
よってゲルを作る場合、架橋密度の高い剛直なゲルを形
成する。In addition, when X is an alcohol residue derived from a polyol such as pentaerythritol or sorbitol, n
is 4 or 6, the crosslinking agent is polyfunctional, and when a gel is made with these, a rigid gel with a high crosslinking density is formed.
またＡがオキシエチレン基の場合には、オキシプロピレ
ン基、オキシブチレン基の場合より架橋剤の親木性は大
きく、オキシエチレン基とオキシプロピレン基もしくは
オキシエチレン基とオキシブチレン基、さらにオキシエ
チレン基とオキシプロピレン基とオキシブチレン基の共
重合体の場合、親水性の程度はそれぞれの成分の比率に
よって代るので、これによって架橋キトサンの親水性の
度合を調整することができる。In addition, when A is an oxyethylene group, the crosslinking agent has a greater affinity for crosslinking than when it is an oxypropylene group or an oxybutylene group. In the case of a copolymer of oxypropylene groups and oxybutylene groups, the degree of hydrophilicity varies depending on the ratio of each component, so the degree of hydrophilicity of crosslinked chitosan can be adjusted by this.
ｍは１〜５００の範囲を取り得るが、ｍが小さいほど、
架橋剤の単位重量当たりの架橋密度は高くなるため、架
橋キトサンは剛直なゲルとなりやすく、かつ架橋剤の親
木性は小さくなる。ｍが５００を越えると、架橋剤の単
位重量当たりの架橋密度が低くなり過ぎ、架橋剤として
の作用が著しく小さくなって実用に適さない。m can range from 1 to 500, but the smaller m is, the more
Since the crosslinking density per unit weight of the crosslinking agent increases, crosslinked chitosan tends to form a rigid gel, and the wood-philicity of the crosslinking agent decreases. When m exceeds 500, the crosslinking density per unit weight of the crosslinking agent becomes too low, and its action as a crosslinking agent becomes extremely small, making it unsuitable for practical use.
なおＹを残基とする二塩基酸は、アルコールのオキシア
ルキレン付加物および酸イミドとのエステル化の容易さ
などから任意に選択される。Note that the dibasic acid having Y as a residue is arbitrarily selected from the viewpoint of ease of esterification with an oxyalkylene adduct of alcohol and an acid imide.
また酸イミドとしては、Ｚの部分構造が一般式［■］お
よびその部分置換体であるフタルイミド、一般式［Ｖ］
およびその部分置換体であるマレイイミド、ならびに一
般式［ＶＩ］およびその部分置換体であるスクシンイミ
ドが工業的に製造し易く、かつ安価であるので望ましい
。In addition, as acid imides, phthalimide whose partial structure of Z is general formula [■] and its partially substituted product, general formula [V]
and its partially substituted product, maleimide, and the general formula [VI] and its partially substituted product, succinimide, are desirable because they are easy to produce industrially and are inexpensive.
本発明の架橋キトサンは、キトサンの希酸水溶液に架橋
剤を加えて十分に混合することにより得られる。The crosslinked chitosan of the present invention can be obtained by adding a crosslinking agent to a dilute aqueous chitosan acid solution and thoroughly mixing the mixture.
キトサンの希酸水溶液は塩酸、酢酸、硫酸などで、ｐＨ
４〜５に調整した水溶液、にキトサンを１〜１０重量％
を加え、十分に撹拌して溶解させる。A dilute acid aqueous solution of chitosan is hydrochloric acid, acetic acid, sulfuric acid, etc. to adjust the pH.
1 to 10% by weight of chitosan in an aqueous solution adjusted to 4 to 5.
Add and stir thoroughly to dissolve.
キ１〜サンと架橋剤との混合割合は１００：１〜５０重
量比である。反応は約２０〜３０℃゛の温度で、デイス
パーで１１００Ｃ）−２００Ｏｒｐ、５分間程度混合し
た後、４０〜６０℃で２〜３時間静置する。The mixing ratio of Ki1 to San and the crosslinking agent is 100:1 to 50 by weight. The reaction is carried out at a temperature of about 20-30°C, and after mixing for about 5 minutes at 1100°C-200°C using a disper, the mixture is allowed to stand at 40-60°C for 2-3 hours.
［発明の効果コ
本発明で得られた架橋キトサンは、新規な高分子化合物
であり、耐熱性および柔軟性に優れていて５人工皮膚な
ど医薬関連分野への用途が期待される。[Effects of the Invention] The crosslinked chitosan obtained in the present invention is a new polymer compound, and has excellent heat resistance and flexibility, and is expected to be used in pharmaceutical related fields such as artificial skin.
［実施例］
つぎに、実施例により、本発明を具体的に説明する。％
は重量％を示す。[Example] Next, the present invention will be specifically explained with reference to Examples. %
indicates weight %.
実施例１
０．５％酢酸水溶液に、キトサンＰ Ｓ Ｈ［焼津水産
（株）商品名、白色粉末、平均分子量：１００００、元
素分析値（理論値）：Ｃ４３，８％（４５，０％）、Ｉ
！６、：ｌ１％（６，８％）、Ｎ ８．８′！、（８，
５％）コを加え、５％水溶液を調整した。Example 1 Chitosan P S H [Yaizu Suisan Co., Ltd. trade name, white powder, average molecular weight: 10000, elemental analysis value (theoretical value): C43.8% (45.0%) in 0.5% acetic acid aqueous solution , I
! 6, :l1% (6,8%), N 8.8'! ,(8,
5%) was added to prepare a 5% aqueous solution.
これに式［Ｘ］で示される架橋剤、Ｐ−６０００［日本
油脂（株）商品名、白色粉末１分子量ニア０００、ｐＨ
： ３，５．水分：０．４４％、元素分析値（理論値）
：ｃ ５３．１％（５３，４％）、８８．９％（８，５
％）。To this, a crosslinking agent represented by the formula [X], P-6000 [trade name of Nippon Oil & Fats Co., Ltd., white powder 1 molecular weight near 000, pH]
: 3,5. Moisture: 0.44%, elemental analysis value (theoretical value)
:c 53.1% (53.4%), 88.9% (8.5
%).
Ｎ Ｏ，７％（０，８％）］ヲキトサン／架橋剤を３１
０．１．３１０．２．３１０．４および３１０．８重量
比でそれぞれ混合し、デスパーを用いて１１０００ｐｐ
、５分間撹拌したのち、ポリエチレン容器（１５Ｘ３０
Ｘ１ｃｍ）に流し込み、４０℃にて３時間反応させて、
乾燥膜厚が３５μｍの皮膜を得た。この皮膜を試験片と
した。NO, 7% (0,8%)] wochitosan/crosslinking agent 31
0.1.310.2.310.4 and 310.8 were mixed at a weight ratio of 11000pp using a desper.
After stirring for 5 minutes, transfer to a polyethylene container (15 x 30
x1cm) and reacted at 40°C for 3 hours.
A film having a dry film thickness of 35 μm was obtained. This film was used as a test piece.
ＣＩ□−〇−町
【
調整し、式［ＸＩ］で示される架橋剤、Ｇ−４９７０［
日本油脂（株）商品名、白色粉末、分子量：５７００、
ｐＨ： ３．８．水分：０．４１％１元素分析値（理論
値）：Ｃ５２，部（５３，４％）４１８．３％（８，５
％）。CI□-〇-machi
Nippon Oil & Fats Co., Ltd. product name, white powder, molecular weight: 5700,
pH: 3.8. Moisture: 0.41% 1 element analysis value (theoretical value): C52, parts (53,4%) 418.3% (8,5
%).
Ｎ Ｏ，８％（０，８％）コをキトサン／架橋剤が３１
０．１．３１０．２．３１０．４および３１０．８重量
比となるようにそれぞれ混合し、実施例１と同様に皮膜
試験片を作成した。NO, 8% (0.8%) and chitosan/crosslinking agent are 31
They were mixed at a weight ratio of 0.1.310.2.310.4 and 310.8, respectively, and a film test piece was prepared in the same manner as in Example 1.
Ｃ１１２−０一連
実施例２
実施例１と同様にして、５％キトサン水溶液をυ
実施例３
実施例１と同様にして、５％キトサン水溶液を調整し、
式〔店コで示される架橋剤、ＡＭ−１０２［日本油脂（
株）商品名、白色粉末、分子ｆｆｉ：３４００、ＰＩ４
： ３．６．水分：０．４６％、元素分析値（理論値）
：Ｃ５３，６％（５３，４％）、１１８．９％（８，５
％）。C112-0 Series Example 2 A 5% chitosan aqueous solution was prepared in the same manner as in Example 1. Example 3 A 5% chitosan aqueous solution was prepared in the same manner as in Example 1.
Cross-linking agent shown by the formula [Shopco], AM-102 [NOF (NOF)
Co., Ltd. product name, white powder, molecule ffi: 3400, PI4
: 3.6. Moisture: 0.46%, elemental analysis value (theoretical value)
:C53.6% (53.4%), 118.9% (8.5
%).
Ｎ００８％（０，８％）］をキトサン／架橋剤が３１０
，１．３１０．２．３１０．４および３７０．８重量比
となるようにそれぞれ混合し、実施例１と同様に皮膜試
験片を作成した。N008% (0.8%)] and chitosan/crosslinking agent is 310
, 1.310.2.310.4 and 370.8 weight ratios, respectively, and coated test pieces were prepared in the same manner as in Example 1.
比較例１
実施例１と同様にして、５％キトサン水溶液を調整し、
ポリエチレン容器（１５Ｘ３０Ｘ１ｃｍ）に流し込み、
４０℃、６００〜７６０ｍｍＨｇで３時間かけて揮発分
を蒸発させ、乾ｍ膜厚が３５μｍの皮膜を得た。この皮
膜を比較試験片とした。Comparative Example 1 A 5% chitosan aqueous solution was prepared in the same manner as in Example 1,
Pour into a polyethylene container (15 x 30 x 1 cm),
Volatile components were evaporated at 40° C. and 600 to 760 mmHg for 3 hours to obtain a film with a dry film thickness of 35 μm. This film was used as a comparative test piece.
上記で得た各試験片について、ゲル分率、破断伸び率、
抗張力および加熱減量の測定を行った。For each test piece obtained above, gel fraction, elongation at break,
Tensile strength and heat loss were measured.
結果を第１表および第２表に示す。また、実施例１で得
られた架橋キトサンの赤外線吸収スペクトル図を第１図
に示す。The results are shown in Tables 1 and 2. Furthermore, an infrared absorption spectrum diagram of the crosslinked chitosan obtained in Example 1 is shown in FIG.
く試験方法〉
ゲル分率：各試験片５乙をとり、０．５％酢酸水溶液１
００ｍ１を加え、ホモミキサーを用いて２０°Ｃで２時
間混合して溶解させた。その後、この溶解液をろ紙でろ
過し、その残さを４０℃３時間乾処
燥茨せてから残さの重量を測定し、試験片重量に対する
残さ重量の割合を％で表した。Test method〉 Gel fraction: Take 5 pieces of each test piece and add 1 piece of 0.5% acetic acid aqueous solution.
00ml was added and mixed using a homomixer at 20°C for 2 hours to dissolve. Thereafter, this solution was filtered through a filter paper, and the residue was dried at 40° C. for 3 hours, then the weight of the residue was measured, and the ratio of the weight of the residue to the weight of the test piece was expressed as %.
引張り試験：各試験片を８０Ｘ １０ｍｍの大きさに切
り、引張り試験機［ストログラフＷ東洋精器（株）製］
を用いて破断伸び率と抗張力とを測定した。Tensile test: Cut each test piece into a size of 80 x 10 mm and use a tensile tester [Strograph W manufactured by Toyo Seiki Co., Ltd.]
The elongation at break and tensile strength were measured using
なお、室温２０’Ｃの室内においておこない引張り速度
は５ ｍｍ／分である。Note that the stretching was carried out indoors at a room temperature of 20'C, and the pulling speed was 5 mm/min.
加熱減量：各試験片１０ｏ＋ｇをとり、 Ｃｕｒｉ
ｅＰｏｉｎｔ Ｐｙｒｏｌｙｓｅｒ［８水分析工業（株
）製］を用いてａｔ！ｌ定した。昇温速度は１０℃／分
、温度範囲は２５〜６００℃とし、加熱減量をＸで表し
た。Heating loss: Take 10o+g of each test piece,
at! using ePoint Pyrolyser [manufactured by 8 Water Analysis Industry Co., Ltd.]. I decided. The heating rate was 10°C/min, the temperature range was 25 to 600°C, and the loss on heating was expressed as X.
第１表から明らかなように、比較例１のキトサンは希酸
水溶液に溶解しゲル分率がゼロ％であるのに対し、実施
例で得られた架橋キトサンはもはや希酸には溶解せず、
高いゲル分率を示した。また、破断伸び率においても、
架橋キトサンはキトサンに比較して高い値を示した。As is clear from Table 1, the chitosan of Comparative Example 1 dissolves in the dilute acid aqueous solution and has a gel fraction of 0%, whereas the crosslinked chitosan obtained in the example no longer dissolves in the dilute acid. ,
It showed a high gel fraction. Also, in terms of elongation at break,
Crosslinked chitosan showed higher values compared to chitosan.
加熱減量においては、第２表で見られるように、特に３
００℃付近で両者の差異が明らかである。As shown in Table 2, in terms of heating loss, especially 3
The difference between the two is obvious at around 00°C.
すなわちキトサンは２００〜３００℃で熱分解と思われ
る変化がＷｔ著であるが、架橋キトサンは熱の影響をよ
り受けにくいことが認められた。That is, chitosan showed a significant change in Wt at 200 to 300° C. that appeared to be due to thermal decomposition, but crosslinked chitosan was found to be less susceptible to heat.
以上のことからキトサンと架橋剤とを反応させてえられ
た架橋キトサンは、もはや希酸水溶液には溶解しない二
次元の高分子化合物であり、柔軟性のある皮膜である。From the above, crosslinked chitosan obtained by reacting chitosan with a crosslinking agent is a two-dimensional polymer compound that no longer dissolves in dilute acid aqueous solution, and is a flexible film.
嗣＠柚
４、図面のｆ！ｌ ｌ−な説明
第１図は、実施例１で得られた キトサン／Ｐ−６００
０＝ ３１０ 、４ （重量比）の架橋キトサンの赤外
線吸収スペクトル図である。Tsugu @ Yuzu 4, f in the drawing! Figure 1 shows the chitosan/P-600 obtained in Example 1.
0=310,4 (weight ratio) is an infrared absorption spectrum diagram of crosslinked chitosan.
Claims (1)
シイミドエステル化合物とを反応させて得られる架橋キ
トサン。 ▲数式、化学式、表等があります▼・・・［ I ］ （ただし式中、 Ｘは炭素数が２〜６で、２〜６個の水酸基を持つ化合物
の残基、 Ａはオキシエチレン基、オキシプロピレン基およびオキ
シブチレン基から選ばれる、１種または２種以上の混合
基、 Ｙは二塩基酸残基、 Ｚは （１）式［II］▲数式、化学式、表等があります▼ およびその部分置換体、 （２）式［III］▲数式、化学式、表等があります▼ およびその部分置換体、 （３）式［IV］▲数式、化学式、表等があります▼ およびその部分置換体、 （４）式［Ｖ］▲数式、化学式、表等があります▼ およびその部分置換体。 （５）式［VI］▲数式、化学式、表等があります▼ およびその部分置換体、 （６）式［VII］▲数式、化学式、表等があります▼ およびその部分置換体、ならびに （７）式［VIII］▲数式、化学式、表等があります▼ およびその部分置換体から選ばれる基、 ｍは１〜５００、 ｎは２〜６ を示す。）[Scope of Claims] 1) Crosslinked chitosan obtained by reacting chitosan with an N-hydroxyimide ester compound represented by the general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...［I］ (However, in the formula, X is the residue of a compound with 2 to 6 carbon atoms and 2 to 6 hydroxyl groups, A is an oxyethylene group, One or more mixed groups selected from oxypropylene group and oxybutylene group, Y is dibasic acid residue, Z is (1) formula [II] ▲ Numerical formula, chemical formula, table, etc. ▼ and its Partially substituted products, (2) Formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and its partially substituted products, (3) Formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and its partially substituted products, (4) Formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and its partially substituted products. (5) Formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and its partially substituted products, (6) Formula [VII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and partially substituted products thereof, and (7) Formula [VIII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and a group selected from its partially substituted products, m is 1 ~500, n indicates 2 to 6.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63335055A JPH02180903A (en) | 1988-12-29 | 1988-12-29 | Crosslinked chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63335055A JPH02180903A (en) | 1988-12-29 | 1988-12-29 | Crosslinked chitosan |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02180903A true JPH02180903A (en) | 1990-07-13 |
Family
ID=18284243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63335055A Pending JPH02180903A (en) | 1988-12-29 | 1988-12-29 | Crosslinked chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02180903A (en) |
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|---|---|---|---|---|
| US6693188B2 (en) | 2001-08-08 | 2004-02-17 | Cargill Incorporated | N-acetyl-D-glucosamine and process for producing N-acetyl-D-glucosamine |
| JP2004359895A (en) * | 2003-06-06 | 2004-12-24 | Mcrotech Kk | Medical composition |
| US6972284B2 (en) | 2000-03-15 | 2005-12-06 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| WO2006016598A1 (en) * | 2004-08-10 | 2006-02-16 | National Institute For Materials Science | Biological low-molecular weight derivative, crosslinked matter and biodegradable and absorbable adhesive material for medical use |
| WO2006016600A1 (en) * | 2004-08-10 | 2006-02-16 | National Institute For Materials Science | Tartaric acid derivative and high-molecular weight crosslinked matter synthesized by using the derivative |
| US7488812B2 (en) | 2002-04-02 | 2009-02-10 | Cargill, Incorporated | Chitosan production |
| US7816514B2 (en) | 2001-02-16 | 2010-10-19 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| JP2011500955A (en) * | 2007-10-30 | 2011-01-06 | ヴィスコゲル アーベー | Chitosan composition |
| US7923437B2 (en) | 2001-02-16 | 2011-04-12 | Cargill, Incorporated | Water soluble β-glucan, glucosamine, and N-acetylglucosamine compositions and methods for making the same |
| US8222232B2 (en) | 2001-02-16 | 2012-07-17 | Cargill, Incorporated | Glucosamine and N-acetylglucosamine compositions and methods of making the same fungal biomass |
-
1988
- 1988-12-29 JP JP63335055A patent/JPH02180903A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6972284B2 (en) | 2000-03-15 | 2005-12-06 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| US7413881B2 (en) | 2000-03-15 | 2008-08-19 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| US7816514B2 (en) | 2001-02-16 | 2010-10-19 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| US8222232B2 (en) | 2001-02-16 | 2012-07-17 | Cargill, Incorporated | Glucosamine and N-acetylglucosamine compositions and methods of making the same fungal biomass |
| US8034925B2 (en) | 2001-02-16 | 2011-10-11 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| US7923437B2 (en) | 2001-02-16 | 2011-04-12 | Cargill, Incorporated | Water soluble β-glucan, glucosamine, and N-acetylglucosamine compositions and methods for making the same |
| US6693188B2 (en) | 2001-08-08 | 2004-02-17 | Cargill Incorporated | N-acetyl-D-glucosamine and process for producing N-acetyl-D-glucosamine |
| US7488812B2 (en) | 2002-04-02 | 2009-02-10 | Cargill, Incorporated | Chitosan production |
| JP4669919B2 (en) * | 2003-06-06 | 2011-04-13 | コスモテック株式会社 | Medical composition |
| JP2004359895A (en) * | 2003-06-06 | 2004-12-24 | Mcrotech Kk | Medical composition |
| WO2006016600A1 (en) * | 2004-08-10 | 2006-02-16 | National Institute For Materials Science | Tartaric acid derivative and high-molecular weight crosslinked matter synthesized by using the derivative |
| WO2006016598A1 (en) * | 2004-08-10 | 2006-02-16 | National Institute For Materials Science | Biological low-molecular weight derivative, crosslinked matter and biodegradable and absorbable adhesive material for medical use |
| JP2011500955A (en) * | 2007-10-30 | 2011-01-06 | ヴィスコゲル アーベー | Chitosan composition |
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